US10982071B2 - Sulfonic acid esters as regulators in radical polymerization reactions - Google Patents

Sulfonic acid esters as regulators in radical polymerization reactions Download PDF

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US10982071B2
US10982071B2 US15/571,949 US201615571949A US10982071B2 US 10982071 B2 US10982071 B2 US 10982071B2 US 201615571949 A US201615571949 A US 201615571949A US 10982071 B2 US10982071 B2 US 10982071B2
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polymerizable composition
regulator
composition according
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Robert Liska
Christian GORSCHE
Konstanze Seidler
Norbert Moszner
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Ivoclar Vivadent AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L57/00—Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to the use of sulfonic acid esters as regulators in radical polymerization reactions.
  • Radical polymers are formed by radical polymerization of one (homopolymer) or more (copolymer) radically polymerizable monomers. Depending on the functionality of the monomers being polymerized, linear polymers (in the case of monofunctional monomers) or cross-linked polymers (in the case of di- or multifunctional monomers) are obtained.
  • radical polymerizations can be performed in bulk (bulk polymerization), solution, suspension or emulsion.
  • radical-forming initiators are added, which form radicals by thermolysis, photolysis or redox reaction. Radical polymerization proceeds according to a chain growth mechanism in which the polymerization-triggering radicals, the so-called primary radicals, are added on to the double bond of the monomers.
  • the initiator radicals formed in this way add on to many other monomer molecules in a rapid growth reaction until the growth of the polymer radicals is terminated by combination or disproportionation and thus the finished macromolecules are formed.
  • chain transfers often occur.
  • the polymer radical abstracts another atom from a second molecule, e.g. from a monomer, solvent or polymer molecule, by homolytic bond cleavage.
  • the newly formed radical on the second molecule can again trigger a polymerization.
  • chain transfer agents so-called regulators or chain regulators, the number average molar mass of the polymer can be regulated in a targeted manner (cf. H. G. Elias, Makromoleküle, vol. 1, 6th edition, Wiley-VCH, Weinheim etc. 199, 299-352).
  • the known chain transfer agents include e.g. the mercaptans, which form thiyl radicals by the transfer of an H atom, which radicals then initiate a new polymerization sequence.
  • double-bond-containing reagents have proved particularly suitable as chain transfer agents, which react according to a radical addition-fragmentation chain transfer (AFCT) mechanism.
  • AFCT radical addition-fragmentation chain transfer
  • Sulfur compounds such as allyl sulfides, allyl sulfones, dithioesters, dithiocarbamates, xanthates and trithiocarbonates are particularly effective as AFCT reagents and have been well studied (Moad et al., Polymer 49, 1079-1131 (2008)).
  • RAFT reagents reversible AFCT reagents
  • RAFT reagents such as e.g. dithioesters, dithiocarbamates, trithiocarbonates or xanthates, are known from controlled radical polymerization (Moad et al., see above; U.S. Pat. No. 5,932,675).
  • the use of the known compounds having transfer activity not only allows the molecular weight of the polymers to be controlled by chain termination in this way, but also undesirably retards the rate at which the polymerization progresses since it retards the chain reaction by temporarily stabilizing the radical.
  • U.S. Pat. No. 2,694,699 further discloses the homo- and copolymerization of a-sulfonoxy acrylates to give “high molecular weight resinous products”.
  • the optional addition of alkylmercaptans as chain regulators is also disclosed.
  • AFCT regulators similar to those described in Moad et al. are outstandingly suitable for use in dental materials, since they provide the polymers thus produced with debonding-on-demand properties, i.e. they make it possible to release adhesive bonds in a targeted manner (e.g. dental retaining clasps in orthodontics, so-called “brackets”).
  • This is achieved by a more homogeneous network with a sharp glass transition, which is attributable to the regulating effect of the transfer reagent.
  • the more homogeneous network also leads to a clear improvement in impact resistance, to a significantly greater extent than with the known materials.
  • the gel point is shifted towards higher conversions during polymerization, leading to lower contraction stresses in the polymers.
  • the object of the invention was to provide chain transfer agents, i.e. regulators, which, while having a regulating effect on chain growth during the polymerization of radically polymerizable, ethylenically unsaturated monomers, do not slow down the rate of reaction to an undesirably great extent.
  • chain transfer agents i.e. regulators
  • the invention achieves this object by providing the novel use of sulfonic acid esters of the following Formula 1 and/or Formula 2—some of which are known per se—individually or as a mixture of more than one thereof as regulators in polymerization reactions of radically polymerizable, ethylenically unsaturated monomers:
  • a in each case independently is selected from H, CN, linear, branched or cyclic aliphatic or aromatic C 1 -C 30 hydrocarbon residues, which are optionally substituted with one or more substituents, wherein the aliphatic hydrocarbon residues are optionally interrupted by one or more urethane groups, ester groups, O and/or S;
  • X in each case independently is —COO— or —CON(R 1 )—, wherein the binding to A occurs via O or N, or is absent if A is an aromatic hydrocarbon residue or CN;
  • B in each case independently is selected from linear, branched or cyclic aliphatic or aromatic C 1 -C 30 hydrocarbon residues, which are optionally substituted with one or more substituents, wherein the aliphatic hydrocarbon residues are optionally interrupted by one or more urethane groups, ester groups, O and/or S;
  • R 1 in each case independently is selected from hydrogen and linear, branched or cyclic aliphatic or aromatic
  • the inventors have surprisingly found that, by formally replacing the carbon atom in the sulfonylallyl groupings of the allyl sulfones and/or sulfonyl methyl acrylates known from Moad et al. (see above) with an oxygen atom, the suitability of the thus obtained vinylsulfonates or sulfonyloxy acrylates, acrylamides or acrylonitriles as regulators is significantly improved, particularly for the polymerization of (other) vinyl esters and (meth)acrylates.
  • the molar ratio between the ethylenic unsaturations in the radically polymerizable monomers and the sulfonate groupings in the sulfonic acid esters of Formulae 1 and 2 acting as regulators is at least 2:1 according to the present invention and in preferred embodiments at least 3:1, more preferably at least 5:1 or at least 10:1, so that the chain lengths are not reduced excessively by the presence of the regulator.
  • ethylenically unsaturated monomers Based on the molecular weight, preferably 50 to 99 wt.-%, more preferably 60 to 98 wt.-%, more preferably 70 to 95 wt.-%, of the ethylenically unsaturated monomers are used, based on the total weight of the monomers and regulators, which depends on the one hand on the substituents A and B in Formula 1 and 2 and on the other hand on the monomers to be polymerized in each case.
  • the solvent preferably used according to the present invention is particularly preferably selected from water, dimethyl sulfoxide, ethanol, dimethylformamide, polyethylene glycol, acetonitrile, THF, methylene chloride, chloroform, benzene and mixtures thereof in order to guarantee a homogeneous solution of the monomers and regulators without impeding chain growth.
  • the ethylenically unsaturated monomers are selected from (meth)acrylates, vinyl esters and mixtures thereof, more preferably from multifunctional (meth)acrylates and vinyl esters, since this is where the present invention—possibly because of the structural similarity of the vinylsulfonates of Formulae 1 and 2—has provided the best results so far.
  • At least one radical polymerization initiator and optionally at least one solvent is used in the polymerization reaction, both of these being preferred, in order to achieve more precise control of the reaction conditions.
  • residue A is selected from hydrocarbon residues with 1 to 20, preferably 1 to 12, carbon atoms.
  • residue A preferably comprises an aliphatic hydrocarbon residue, which is optionally interrupted by 1 to 4 urethane groups, ester groups or oxygen atoms, preferably oxygen atoms, and is optionally substituted with 1 to 4 OH groups.
  • the residues A and/or B preferably further comprise at least one phenyl, phenylene, naphthyl or naphthylene residue, preferably 1 to 4, more preferably 1 or 2, phenyl or phenylene residues, wherein the at least one phenyl, phenylene, naphthyl or naphthylene residue is more preferably substituted with 1 to 3 substituents selected from —OH, —CH 3 and —OCH 3 .
  • the residues R 1 are preferably aliphatic C 1-6 hydrocarbon residues, which are optionally interrupted by 1 to 2 oxygen atoms and optionally substituted with 1 to 2 OH groups.
  • X is preferably either i) —COO—, in which case the binding to A occurs via O, i.e. the sulfonyloxy grouping in the sulfonic acid esters of Formula 1 or 2 is either bound in a position to the carboxyl group of an acrylate, or ii) X is absent, in which case A is an aromatic hydrocarbon residue with 6 carbon atoms, which is optionally substituted with 1 to 3 substituents selected from —CH 3 , —OH and —OCH 3 , with the result that the compounds of Formulae 1 and 2 each represent a vinylsulfonate substituted with A.
  • the regulator acts as a linkage point between two growing polymer chains and therefore on average doubles the molecular weight of the chains, and in the case of n>2 the polymer chain branches at the point of the regulator in a star shape.
  • more than 4 chain strands emanating from one point can be disadvantageous, particularly in terms of the production of cross-linked polymers, since in this way the cross-link density can be undesirably high.
  • R 1 is selected from C 1-10 alkyl.
  • Particularly preferred sulfonic acid esters of Formulae 1 and 2 are selected from the following:
  • the invention relates to a polymer that has been obtained by radical polymerization using sulfonic acid esters of Formula 1 and/or Formula 2 as defined above and which, owing to the presence of the regulator at the chain ends, exhibits a characteristic structure, as will be explained in more detail below. It is preferably a cross-linked polymer.
  • compositions produced according to the invention using sulfonic acid esters of Formula 1 and/or 2 and polymers obtained therefrom may be used advantageously for a variety of applications, and therefore in a third aspect the invention also relates to the use of these cross-linked polymers as varnishes, coatings or adhesives or for the production of shaped bodies by casting or 3D printing.
  • FIG. 1 shows a photo of a bending test with a polymer according to the invention
  • FIGS. 2 a and 2 b each show a photo of a contraction test
  • FIGS. 3, 4 a and 4 b each show a photo of the fractured surface of a polymer.
  • the chain lengths and in some cases also the network structure can be controlled in the polymerization of mono- and multi-functional, ethylenically unsaturated monomers, in particular of (meth)acrylates and vinyl esters, and mixtures thereof.
  • they result in polymer networks with a narrower glass transition, i.e. the glass transition occurs in a narrower temperature range.
  • more homogeneous polymer networks are obtained, i.e. networks that are characterized in that they exhibit a narrower distribution of the molar mass between the cross-linking points. This has the advantage that chain stresses are better able to be relieved by relaxation processes and e.g. more rapid debonding-on-demand (DoD) can be achieved.
  • DoD debonding-on-demand
  • the compounds of Formulae 1 and 2 significantly reduce the glass transition temperature of the polymers in the polymerization of (meth)acrylates without reducing the mechanical properties at room temperature and the rate of polymerization to any significant extent.
  • a reduced glass transition temperature has the advantage that the polymers can be softened at lower temperatures. In the case of adhesives and cements, for example, this allows the adhesive bond to be released in a targeted manner (i.e. debonding-on-demand).
  • the polymer materials obtained are characterized by improved impact resistance, which is highly advantageous e.g. for stereolithographically produced shaped bodies (e.g. 3D printing, rapid prototyping).
  • the compounds of Formulae 1 and 2 cause a marked retardation of gel formation compared with the unregulated reaction during the cross-linking polymerization of e.g. multifunctional (meth)acrylates or vinyl esters, and thus ensure a longer gel time, i.e. that the three-dimensional polymer network is not formed until later.
  • the prolonged gel time has a favourable effect on polymerization contraction stress (PCS), because a longer time is available for internal stresses to be compensated for by flow processes, which is highly advantageous in the case of complex geometries of shaped parts, for instance.
  • PCS polymerization contraction stress
  • the sulfonate esters according to the present invention do not retard the polymerization to anywhere near the same extent as was previously the case with the sulfonyl methyl acrylates or allyl sulfones known from Moat et al. (see above), as clearly demonstrated by the specific examples below.
  • At least one multifunctional monomer more preferably at least one multifunctional (meth)acrylate or vinyl ester, in particular a mixture of mono- and multifunctional monomers, is used as radically polymerizable monomer.
  • monofunctional monomers is meant compounds with one, by polyfunctional monomers compounds with two or more, preferably 2 to 4, radically polymerizable ethylenic unsaturations.
  • compositions according to the present invention comprise at least one dimethacrylate or a mixture of mono- and dimethacrylates.
  • Materials containing mono- and multifunctional (meth)acrylates as radically polymerizable monomers are particularly suitable as adhesives, varnishes, printing inks and for 3D printing.
  • Examples of particularly suitable mono- and multifunctional (meth)acrylates are methyl, ethyl, 2-hydroxyethyl, butyl, benzyl, tetrahydrofurfuryl or isobornyl (meth)acrylate, p-cumylphenoxyethylene glycol methacrylate (CMP-1E), bisphenol A di(meth)acrylate, bis-G(M)A (an addition product of (meth)acrylic acid and bisphenol A diglycidyl ether), ethoxylated or propoxylated bisphenol A di(meth)acrylate, such as e.g.
  • thermo- or photolabile di(meth)acrylates such as e.g. the addition product of 2 mol 2-acetoacetoxyethyl methacrylate and 1 mol 2,2,4- or 2,4,4-trimethylhexamethylene-1,6-diisocyanate (thermolabile) or methacrylic acid 2-[2-(4- ⁇ 2-methyl-2-[2-(methacryloyloxy)ethylcarbamoyloxy]propionyl ⁇ phenoxy)ethoxy-carbonylamino]ethyl ester.
  • thermo- or photolabile monomers and compounds of Formula 1 or 2 are particularly suitable for materials with debonding-on-demand properties.
  • benzophenone benzoin and derivatives thereof or a-diketones or derivatives thereof, such as e.g. 9,10-phenanthrenequinone, 1-phenylpropane-1,2-dione, diacetyl or 4,4′-dichlorobenzil are used.
  • camphorquinone (CQ) and 2,2-dimethoxy-2-phenylacetophenone and quite particularly preferably a-diketones combined with amines as reducing agents are used, such as e.g.
  • EDMAB 4-dimethylaminobenzoate
  • N,N-dimethylaminoethyl methacrylate N,N-dimethyl-sym.-xylidine or triethanolamine.
  • Norrish type-I photoinitiators are also highly suitable, especially acyl or bisacyl phosphine oxides and in particular monoacyltrialkyl- and/or diacyldialkyl-germanium compounds, such as e.g. benzoyltrimethylgermanium, dibenzoyldiethyl-germanium or bis(4-methoxybenzoyl)diethylgermanium (MBDEGe).
  • MBDEGe 4-dimethylaminobenzoate
  • Mixtures of the different photoinitiators such as e.g. bis(4-methoxybenzoyl)diethylgermanium combined with camphorquinone and ethyl 4-dimethylaminobenzoate, can also be used advantageous
  • thermal initiators such as for instance azo compounds, e.g. azobisisobutyronitrile, or peroxides, e.g. dibenzoyl peroxide, as well as benzopinacol and 2,2′-dialkylbenzopinacols are particularly suitable.
  • redox initiator redox initiator combinations
  • redox initiator such as e.g. combinations of benzoyl peroxide with N,N-dimethyl-sym.-xylidine or N,N-dimethyl-p-toluidine
  • redox systems consisting of peroxides and reducing agents of this type, such as e.g. ascorbic acid, barbiturates or sulfinic acids, are also particularly suitable.
  • organic or inorganic particulate fillers are additionally added during the polymerization.
  • Mixtures containing monomers and fillers are referred to as composites.
  • fillers based on oxides with a particle size of 0.010 to 15 ⁇ m such as SiO 2 , ZrO 2 and TiO 2 or mixed oxides of SiO 2 , ZrO 2 , ZnO and/or TiO 2 , nanoparticulate or microfine fillers with a particle size of 10 to 300 nm, such as pyrogenic silicia or precipitated silicia as well as glass powder with a particle size of 0.01 to 15 ⁇ m, preferably of 0.2 to 1.5 ⁇ m, such as quartz, glass-ceramic or radiopaque glass powders of e.g.
  • barium- or strontium-aluminium silicate glasses and radiopaque fillers with a particle size of 0.2 to 5 ⁇ m, such as ytterbium trifluoride, tantalum(V) oxide, barium sulfate or mixed oxides of SiO 2 with ytterbium(III) oxide or tantalum(V) oxide. Fibrous fillers, nanofibres or whiskers are also not excluded. Unless otherwise stated, all particle sizes are weight-average particle sizes.
  • the fillers are categorized as macrofillers or microfillers according to particle size.
  • Macrofillers are obtained by grinding quartz, radiopaque glasses, borosilicates or ceramics, are purely inorganic by nature and generally consist of splinter-shaped parts.
  • Preferred are macrofillers with an average particle size of 0.2 to 10 mm.
  • microfillers preferably pyrogenic SiO 2 or precipitated silicia is used, or mixed oxides, e.g. SiO 2 —ZrO 2 , which can be obtained by hydrolytic co-condensation of metal alkoxides.
  • the microfillers preferably have an average particle size of approx. 5 to 100 nm.
  • SiO 2 -based fillers can be surface-modified with (meth)acrylate-functionalized silanes.
  • silanes is 3-(meth)acryloyloxypropyltrimethoxysilane.
  • non-silicate fillers e.g. of ZrO 2 or TiO 2
  • functionalized acidic phosphates such as e.g. 10-(meth)acryloyloxydecyl dihydrogen phosphate, can also be used.
  • Filling composites preferably have a filler content of 75-90 wt.-% and composite cements 50-75 wt.-%.
  • the polymers according to the invention can in some preferred embodiments comprise e.g. 0 to 90 wt.-%, preferably 0 to 80 wt.-% and particularly preferably 0 to 70 wt.-% filler(s), based on the total weight of all components that are contained, wherein the filler content is adjusted according to the planned use of the polymers as described above.
  • the reaction mixtures may optionally also contain further additives, especially stabilizers, colorants, active microbicidal substances, blowing agents, optical brighteners, plasticizers or UV absorbers, e.g. in a quantity of 0 to 5 wt.-%, preferably 0 to 3 wt.-% and particularly preferably 0.2 to 3 wt.-%, based on the total weight of all components that are contained.
  • further additives especially stabilizers, colorants, active microbicidal substances, blowing agents, optical brighteners, plasticizers or UV absorbers, e.g. in a quantity of 0 to 5 wt.-%, preferably 0 to 3 wt.-% and particularly preferably 0.2 to 3 wt.-%, based on the total weight of all components that are contained.
  • the polymers according to the invention can advantageously also contain one or more solvents, preferably 0 to 80 wt.-%, particularly preferably 0 to 60 wt.-% and in particular 0 to 40 wt.-% solvent, based on the total weight of all components that are contained.
  • solvents are water, ethanol, polyethylene glycol and mixtures thereof.
  • polymers that only contain components which are explicitly mentioned herein. Furthermore, polymers are preferred in which the individual components are each selected from the preferred and particularly preferred substances named herein. Moreover, polymers which, apart from the compounds of Formula 1 and 2, contain no other sulfur compounds and in particular no volatile mercaptans, i.e. compounds having a typical mercaptan odour, are particularly preferred.
  • the polymers produced according to the invention have similar mechanical properties (flexural strength and modulus of elasticity) to dimethacrylate-based materials, but are characterized by reduced polymerization contraction stress (PCS), improved impact resistance and low inherent odour.
  • PCS polymerization contraction stress
  • reaction mixtures of this type and the polymers produced therefrom are suitable for a large number of applications, such as e.g. as varnishes or coatings on various surfaces, e.g. as decorative coatings and protective coats on wood, paper, cardboard and in particular plastics, ceramics or metal.
  • the low polymerization retardation in particular is advantageous here, while the toughness and thus the resistance of the coatings to external mechanical influences can be improved significantly.
  • they can be used as adhesives for bonding a wide variety of materials, or for the production of shaped bodies by casting, compression moulding, rapid prototyping or 3D printing.
  • the improved impact resistance now allows these materials to come up to the same level as common thermoplastics.
  • the low retardation is essential in curing for 3D printing.
  • a particularly preferred application of the materials according to the invention is in the field of the 3D printing of ceramic powders by means of lithography-based methods.
  • the photopolymer produced according to the invention represents the sacrificial structure in the sintering process. The tendency to crack can be reduced by the more homogeneous network.
  • tissue regeneration Another significant use of the materials according to the invention is in the field of tissue regeneration.
  • both hydrogels e.g. from compositions with a low monomer content in water
  • so-called “PEG gels” i.e. with polyethylene glycol as solvent
  • rigid elastic bodies e.g. from solvent-free compositions with a high proportion of polyfunctional monomers
  • tissue supports e.g. for heart valves, as a base material for shunts and stents and as adhesives and closures (e.g. patches) for tissue damage caused by injury or genetically.
  • Triethylamine (TEA, 24.23 g, 0.24 mol) was added to a solution of ethyl pyruvate (23.22 g, 0.20 mol) in dichloromethane (200 ml) at ⁇ 5° C.
  • Methanesulfonyl chloride (27.49 g, 0.24 mol) was added dropwise. After this, the reaction mixture was stirred first for 1 h at ⁇ 5° C. and then stirred further at ambient temperature. After 22 h the yellow reaction solution was washed with water (5 ⁇ 100 ml) and saturated aqueous NaCl solution (100 ml), dried over anhydrous Na 2 SO 4 , filtered and concentrated on a rotary evaporator. The crude product was purified by column chromatography (SiO 2 , n-hexane/ethyl acetate 9:1), wherein 14.99 g (39% of theory) of 1 was obtained as a yellowish liquid.
  • Elemental analysis for C 12 H 18 O 8 calculated C 49.65; H 6.25; found C 49.16; H 6.45.
  • Triethylene glycol dipyruvate (5.81 g, 20.0 mmol), p-toluenesulfonyl chloride (9.53 g, 50.0 mmol) and N,N-dimethylaminopyridine (0.36 g, 3.0 mmol) were dissolved in dichloromethane (100 ml), and triethylamine (7.29 g, 72.0 mmol) was added dropwise.
  • the reaction mixture was stirred for 24 h at RT, washed with water (3 ⁇ 100 ml) and saturated aqueous NaCl solution (100 ml), dried over Na 2 SO 4 , filtered and concentrated on a rotary evaporator.
  • the brown oil was dissolved in n-hexane/ethyl acetate 1:1 (25 ml) and dichloromethane (5 ml) and filtered through a layer of silica gel (SiO 2 , n-hexane/ethyl acetate 1:1). The filtrate was concentrated on a rotary evaporator. Diethyl ether (100 ml) was added to the brownish oil, wherein a brownish precipitate formed. This was filtered off, purified further by repeated digestion with diethyl ether and dried in a vacuum-drying cabinet, wherein 3.64 g (30% of theory) of 3 was obtained as a white solid.
  • Triethylamine (15.69 g, 0.155 mol) was added to a solution of triethylene glycol dipyruvate (5.19 g, 17.9 mmol) in dichloromethane (100 ml) at ⁇ 5° C., and methane-sulfonyl chloride (17.76 g, 0.155 mol) was added dropwise.
  • the reaction mixture was stirred first for 1 h at ⁇ 5° C. and then stirred further at ambient temperature. After 24 h the yellowish-brown reaction solution was washed with water (5 ⁇ 100 ml) and saturated aqueous NaCl solution (100 ml), dried over Na 2 SO 4 , filtered and concentrated on a rotary evaporator.
  • the crude product was purified by column chromatography (SiO 2 , n-hexane/acetone 3:2), wherein 1.69 g (3.8 mmol; 21% of theory) of 5 was obtained as a yellowish liquid.
  • a Netzsch DSC 204 F1 with autosampler was used for the polymerization. The measurement was carried out isothermally at 25° C. under a nitrogen atmosphere. 10 ⁇ 1 mg of sample mixture were weighed into an aluminium DSC pan which was placed in the DSC chamber using the autosampler. The sample was flushed with nitrogen (20 ml/min) for 4 min and then irradiated for 5 min using filtered UV light (400-500 nm; Omnicure 2000) with an intensity of 1 W/cm 2 at the beam output of the lamp. The time taken to reach 95% of maximum conversion (t 95 ) and the time taken to reach the maximum rate of polymerization (t max ) were used to evaluate the reactivity.
  • samples were also produced with monofunctional benzyl methacrylate (BMA).
  • BMA monofunctional benzyl methacrylate
  • the samples were also flushed with nitrogen (20 ml/min) for 4 min and then irradiated for 5 min using filtered UV light (400-500 nm; Omnicure 2000) with an intensity of 1 W/cm 2 at the beam output of the lamp.
  • the polymerized samples were dissolved in THF and analysed with a Waters GPC with three columns connected in series (Styragel HR 0.5, Styragel HR 3 and Styragel HR 4) and a Waters 2410 RI detector in a column oven at 40° C. and at a flow rate of 1.0 ml/min.
  • the ratio between the number-average molecular weight of the modified polymer and that of pure poly-BMA shows how far the average molecular weight is reduced by the regulator.
  • a marked reduction in molecular weight i.e. a low value of the Mn mod /Mn BMA ratio, is desirable together with a high rate of polymerization, i.e. relatively low values for t 95 and t max in the above reaction with UDMA/D 3 MA.
  • DBC U/D The double bond conversion for the UDMA/D 3 MA monomer mixture is referred to below as DBC U/D and that for the BMA monomer alone as DBC BMA .
  • compounds 1 and 2 according to the present invention were compared with, among others, those that were known from Moad et al. (see above) and from earlier research by the inventors, including compound 4, as well as other transfer reagents.
  • Comparison example 1 involved either the pure methacrylate-based mixture of equal parts by weight of UDMA and D 3 MA or monofunctional methacrylate BMA.
  • Comparison example C2 is composed of a mixture of C1 and the ⁇ -allyl sulfone 4, which was used as an analogue to compound 2.
  • C3 to C 12 are comparison examples from methacrylates (based on either UDMA/D 3 MA or BMA) with a wide variety of known regulators, which are differentiated on the basis of their leaving group (sulfone, sulfide, phosphono, alkyl) or activating group (ester, amide, aromatic).
  • C13 involves a formulation with a Barton ester as regulator.
  • the formulations that were produced were measured with an MCR302 WESP photorheometer from Anton Paar, which was connected to a Bruker Vertex-80 IR spectrometer to monitor conversion.
  • a PP-25 measuring system was used and the measuring gap was adjusted to 0.1 mm.
  • the storage and loss modulus of the samples were measured in oscillation mode (1% deflection, 1 Hz).
  • IR spectra of the sample were recorded during the measurement at a frequency of approx. 5 Hz.
  • formulations produced in the same way as in the above Examples 6 and 7 and comparison examples 14 and 15 were poured into silicone moulds and polymerized in a light furnace (Lumamat 100 model, Ivoclar AG) using programme 2 (10 min irradiation with an intensity of approx. 20 mW/cm 2 ). The bars were turned and cured again. The sample bars were polished and then measured using an Anton Paar MCR301 rheometer with a CTD (convection temperature control) oven and an inserted solid rectangular fixture (SRF12 for rectangular cross-sections of up to 12 mm). The rate of heating was set at 2° C./min. All the samples were heated up from ⁇ 100° C. to 200° C.
  • Table 3 gives the results for the determination of the storage modulus at room temperature (G′ (20° C.) ), the glass transition temperature (T G ) and the full width at half maximum (FWHM) of the loss factor curve at glass transition.
  • test bars (1 ⁇ 0.45 ⁇ 0.15 cm) were made from formulations analogous to the above
  • formulations were produced with GDVA monomer alone (comparison example 20) and with 24 wt.-% of compounds 2 (Example 12) and 4 (comparison example 21) respectively. All three formulations additionally contained approx. 0.5 wt.-% Ivocerin (Ivoclar Vivadent) as photoinitiator.
  • the photoreactivity was checked in the same way as in Examples 6 and 7 and comparison examples 14 and 15 above. Again, the time taken to reach the gel point (intersection of storage and loss modulus) and the time taken to reach 95% of total conversion (t 95% ) were used as a measure of photoreactivity.
  • test pieces made of pure GDVA could be broken with this test configuration while the test pieces produced according to the present invention with 24 wt.-% of compound 2 exhibited such high toughness that they withstood the impact bending test undamaged.
  • Formulations were produced with polyethylene glycol diacrylate (PEGDA, Mw approx. 750 g/mol) alone (comparison example 23) and with 19 wt.-% of compounds 2 (Example 14) and 4 (comparison example 24) respectively. All the formulations additionally contained approx. 0.5 wt.-% Ivocerin as photoinitiator.
  • the resin formulations produced were mixed with 60 wt.-% dimethyl sulfoxide (DMSO) and, to check the photoreactivity, these formulations were measured in the same way as in Example 6 with an MCR302 WESP photorheometer from Anton Paar, which was connected to a Bruker Vertex-80 IR spectrometer to monitor conversion. The results obtained are listed in Table 7.
  • the reduced contraction stress measured after adding compound 2 was illustrated in the following way: an optical analysis of the polymerization contraction was performed, to which end the DMSO-based PEGDA formulations with compound 2 as regulator were poured into a Teflon mould and irradiated in a Lumamat 100 for 10 min.
  • FIG. 2 shows the gels obtained in this way.
  • Formulations were produced with the urethane diacrylate (UDA) Ebecryl 2002 from Sartomer alone (comparison example 25) and with 20 wt.-% of compounds 2 (Example 15) and 4 (comparison example 26) respectively. All the formulations additionally contained approx. 1 wt.-% Darocur 1173 (BASF) as photoinitiator. To check the photoreactivity these formulations were measured in the same way as in Examples 6 and 7 with an MCR302 WESP photorheometer from Anton Paar, which was connected to a Bruker Vertex-80 IR spectrometer to monitor conversion. The results obtained are listed in Table 8.
  • UDA urethane diacrylate
  • BASF Darocur 1173
  • An anodized aluminium foil was coated with formulations produced in the same way as in the above examples with UDA as monomer and 10 and 20 wt.-% regulator, respectively (4-mil doctor blade, approx. 102 ⁇ m) and cured in a UV oven.
  • the coatings were cut using a cross-cut tester (6 ⁇ 2 mm) and then adhesive tape (Tesafilm Standard 19 mm) was stuck evenly over the cut coatings. The adhesive tapes were pulled off evenly at an angle of approx. 60° and the appearance of the remaining grid was evaluated. Table 9 shows the results obtained from this test.
  • the UDA-based coating without regulator from comparison example 27 exhibited a number of detached squares, whereas for all the coatings produced with regulator—both with 10 wt.-% and with 20 wt.-% regulator—only small flakes of the coating were detached at the intersections and cut edges of the grid lines.
  • regulator both with 10 wt.-% and with 20 wt.-% regulator—only small flakes of the coating were detached at the intersections and cut edges of the grid lines.
  • the effect of compounds 2 and 4 as regulator was equivalent in this respect.
  • Diagram 1 below shows the reaction sequence for the reaction without BMA in comparison example 30 confirmed by NMR.
  • Sulfonate ester compounds of Formulae 1 and 2 are therefore incapable of any homopolymerization, since their vinylic or acrylic double bond does not enter into a chain growth reaction, but a fragmentation of the molecule already takes place beforehand with homolytic cleavage of the S—O bond resulting in a shift of the radical position from C to S.
  • the fragmented regulator molecule on the one hand therefore initiates the chain growth of the acrylate monomers, but also terminates it by means of a transfer reaction.
  • the weight-average molecular weight of the polymer obtained in Example 18 in this test was about 1500 g/mol, corresponding to a value for n in the above diagram of about 6. This value can of course be controlled by a suitable selection of the quantitative ratios.
  • the vinyl group of the regulator 2 does not participate in the chain growth reaction of the acrylate monomers, but is in turn converted into a keto group in the course of the fragmentation of the molecule, wherein one fragment of the regulator molecule terminates the chain and the other (the sulfonyl radical) produces another growing chain by addition to a BMA molecule.
  • the sulfonoxy acrylate is intended to act not as a regulator, but (allegedly) as a comonomer, which is why in all three examples it was used in molar ratios of sulfonoxy acrylate (ethyl ⁇ -benzenesulfonoxy acrylate or ethyl ⁇ -methanesulfonoxy acrylate, i.e. compound 1) to actual monomer (methyl acrylate, methyl methacrylate, styrene, acrylonitrile) of about 1:1.
  • reaction mixtures based on an aliphatic polyester urethane methacrylate (Bomar XR 741) with 1 wt.-% Ivocerin® as photoinitiator were produced.
  • As regulators, 5, 7 and 10 wt.-% of compound 2 were added.
  • test bars of type 5B according to DIN EN ISO 527-2 were then printed and tensile tests were carried out using a Zwick-500 tensile testing machine.
  • the results given in Table 10 each represent averages of at least 6 measurements.
  • test bars were polished and then tested using a DYNSTAT configuration according to DIN 53435, wherein the test pieces were unnotched, using a 5 kpcm hammer as in Examples 3 and 4.
  • the fractured surfaces were then analysed by means of SEM using an XL-30 SEM from Philips. For this, the samples were fixed on a sample holder with tape and the edges were coated with a conductive silver solution. The samples were then sputtered with a thin conductive gold layer. Images of the fractured surfaces were captured in 500 ⁇ magnification.
  • FIG. 3 shows the fractured surface of the polymer from comparison example 32, which had been produced without adding any regulator: an extremely smooth fractured surface, which therefore indicates a brittle fracture.
  • FIG. 4 the fractured surfaces of the polymers according to the invention from Example 22 ( FIG. 4 a ) and Example 23 ( FIG. 4 b ) can be seen, which are substantially more ductile then the unregulated dimethacrylate network.
  • regulators of Formula 1 and/or 2 are suitable for the production of the most diverse polymers, as already discussed above.
  • General instructions for the production of formulations for specific applications follow below.
  • Quantity Component Type (parts by weight) Monomer Dimethacrylates, e.g. polyester urethane 100 dimethacrylate Bomar XR 741 Regulator Compound 6 12 Initiator Photoinitiator, such as a bisacyl- 1 germanium compound, e.g. Ivocerin Additives UV absorber, e.g. Sudan Yellow 0.2
  • urethane methacrylates particularly good storage stability is achieved.
  • the long-wave absorption of the photoinitiator is adapted to the emission spectrum of the 3D printer.
  • the UV absorber prevents scattered light and controls the layer thickness of the curing.
  • the sugar-based vinyl ester Through the use of the sugar-based vinyl ester, particularly good biocompatibility is achieved.
  • the degradation products (glucidol, adipic acid and oligovinyl alcohol) have excellent biocompatibility.
  • the filler tricalcium phosphate brings about improved cell adhesion and remodelling.
  • a two-component injection paste can be produced which cures within 30 to 60 min and gives mechanical properties similar to those of bone.
  • the brittleness can be reduced by up to a factor of 10.
  • polyethylene glycol in the base monomer brings about good water solubility and, through the vinyl ester as reactive group, particularly high biocompatibility is achieved.
  • the free carboxyl groups of the regulator also provide good solubility in the PBS buffer (phosphate-buffered sodium chloride solution) for this reagent.
  • Formulations of this type are particularly suitable for forming hydrogel networks in the presence of tissue or living cells. Through the use according to the invention of the regulator, the brittleness of such hydrogels can be reduced significantly.
  • multifunctional acrylates and aromatic urethane diacrylate provides a good basis for tough, abrasion-resistant stamp materials.
  • the brittleness and abrasion resistance of the stamp can be further improved significantly.
  • considerably more accurate reproduction of surface detail can be achieved.
  • This material is also suitable as an imprint material, to which end the proportions of the reactive diluent can be reduced e.g. to about 5 parts by weight.
  • oligomeric acrylates Through the use of the oligomeric acrylates, appropriate reactivities and mechanical properties are achieved. Initiator and pigment are matched in terms of their absorption behaviour. Through the addition according to the invention of the regulator, the brittleness of the printing ink can be reduced without decreasing the reactivity.
  • silicone acrylates Through the use of the silicone acrylates, very good silicone release coatings can be produced.
  • a disadvantage is the ageing behaviour, where the adhesive of the labels can react with unreacted acrylates and therefore poor release characteristics are obtained.
  • the double bond conversion of the coating can be increased significantly without decreasing the reactivity.
  • urethane acrylates particularly good adhesion is achieved, which is advantageous especially in the coating of metal surfaces.
  • This effect can be further reinforced by including regulators such as e.g. compound 3.
  • regulators such as e.g. compound 3.
  • the presence of the reactive diluent acting as a comonomer additionally brings about a reduction in processing viscosity and an improvement in mechanical properties.

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EP15166848.0A EP3091037A1 (fr) 2015-05-07 2015-05-07 Acide sulfonique en tant que régulateur dans des réactions de polymérisation radicalaire
PCT/EP2016/059787 WO2016177677A1 (fr) 2015-05-07 2016-05-02 Ester d'acide sulfonique faisant office de régulateur dans des réactions de polymérisation par voie radicalaire

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EP3090722B1 (fr) * 2015-05-07 2019-01-09 Ivoclar Vivadent AG Matériau dentaire durcissable par polymérisation avec réaction de transfert
ES2767850T3 (es) * 2017-07-06 2020-06-18 Ivoclar Vivadent Ag Materiales poliméricos con reactivos de transferencia a base de silano
JP2019178288A (ja) * 2018-03-30 2019-10-17 太陽インキ製造株式会社 インクジェット印刷用の硬化性組成物、その硬化物及びその硬化物を有する電子部品
TWI798395B (zh) * 2018-03-30 2023-04-11 日商太陽油墨製造股份有限公司 噴墨印刷用之硬化性組成物、其之硬化物及具有該硬化物之電子零件
JP7112170B2 (ja) * 2018-03-30 2022-08-03 太陽インキ製造株式会社 インクジェット印刷用の硬化性組成物、その硬化物及びその硬化物を有する電子部品
EP3659575A1 (fr) * 2018-11-28 2020-06-03 Ivoclar Vivadent AG Composite dentaire photopolymérisable à durcissement rapide et à faible rétractation
WO2022157112A1 (fr) 2021-01-19 2022-07-28 Evonik Operations Gmbh Compositions durcissables par rayonnement pour la fabrication additive d'objets résistants

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EP3292157B1 (fr) 2019-04-24

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